Petroleum wax alkylated phenol and a process of making it



Patented 27,-. I

2,191,499 a rsraomum wax AIKYLA'I'ED rumor.

AND A raoosss oruaxmc rr Orland M. Reifl, Woodbury, n. 3., asaignor to Sooony-Vacnnm Oil Company, New York, N. Y., a corporation of New York No Drawing; Original application'November 27,

1935, Serial No. 51,969.

Divided and this al plication March 26, 1931, Serial No. 133,210 20 Claims. (cl. zoo-6:4)

This invention relates to the production of certain new chemical compositions which may .be generally designated as orwaromatic compounds substituted in their aryl nuclei by long chain alkyl radicals. More particularly, the present invention relates to the production of a, class of compounds of this general type that are stable 'at relatively high temperatures and which in manyinstances are suitable for use in wax con- 10 taining hydrocarbon oils as pour point depressants.

According to Patent 1,815,022, granted to Garland H. B. Davis on July 14, 1931, naphthalene may be condensed with chlorinated wax by mixing the naphthalene with an equal weight of aluminum chloride and then slowly adding the chlorinated wax at a temperature of 140 to 160 F. and finally raising the temperature to around 200 F. to expel the hydrochloric acid formed.

a; The aluminum chloride may then be settled out of the final product. The result of such a reaction appears to be the production of an alkylated naphthalene, which is suillciently stable so that it will not be decomposed by the temperatures 5 ordinarily encountered, when it is used as a pour point depressant in lubricating oils in automobile engines and the like.

In searching for other materials that might be more advantageously used to depress the pour a, point of wax containing hydrocarbon oils, attempts were made .to form wax substituted phenolic compounds by methods similar to those described in the Davis patent, but the results were notencouraging. The compositions formed not 3 only lack the ability to depress the pour point of oil but were found to be quite unstable under ordinary conditions of use, and rapidly decomposed into their component'parts.

It has now been discovered that particularly 40 when phenol and chlorinated paraflln wax are used as the starting ingredients, a stable, relatively pure material, which is particularly effective as a pour point depressant can be made by following the principles which are about to be 4,5 described. Although it is believed that the principles of' this invention are applicable not only to the formation of wax substituted phenol, but

also to the formation of alkyl substituted oxyaromatic substances in general, the invention will 50 nevertheless be described as it has been applied to the manufacture of parailln wax substituted phenol, and the possible extension of' the invention to the manufacture of other alkylated onaromatic materials will be discussed later. u According to this invention it has been discovered that if a reaction between the phenol, chlorinated wax and'aluminum chloride is carried out merely by heating the, reactants slowly'until the evolution of hydrochloric acid gas ceases, the aluminum of the'aluminum chloride '6 I merely replaces the hydrogen on the OH group of the phenol and the chlorine, combining with this hydrogen, forms hydrochloric acid. Thus the product so formed is mostly a mixture of an aluminum phenate type of compound, perhaps 10 containing some chlorine, and unreacted phenol and chlorinated wax.

It has also been found, that if instead of terminating the reaction at the point where the first evolution of hydrochloric acid gas ceases, .15

the temperature be further raised and an additional evolution of hydrochloric acid thus caused to take place, a wax substitution will take place but the aluminum will still remain as a part of the compound. For example, when using around 3% aluminum chloride, if the temperature is raised to about 350 F. to complete the reaction, the product at the end'of thereaction and before further treatment contains a considerable amount of wax substituted aluminumphenate. Further than the step of heating to complete the reaction, which is one important step in this invention, it has also been discovered that the wax substituted aluminum phenate type of compound can be converted into the desired wax substituted phenol and. freed from aluminum both as a part of the compound and as interbe readily understood from the following detailed description of the new process. A skilled chemistwill, of course, see numerous places where minor variations can be made, but any radical departure from the detailed instructions hereafter set forth is almost certain to result in a failure to produce the preferred type of product according to this invention.

In the first place, the reagents used are phenol, chlorinated wax and anhydrous aluminum chloride. The phenol, CaHsOH, should be substanbe derived from another source, it will usually be a petroleum wax. With the wax melted and heated to about 200 F., chlorine can be bubbled through until the desired amount, about 14%, is absorbed. Higher temperatures hasten this reaction, but if too high areJikely to darken the product.

The degree of chlorination of the chlorwax is of considerable importance. As the chlorine content of the wax increases, the depressant eflect of the product increases, but simultaneously, two detrimental characteristics develop. The product tends to become harder'and less soluble in oil. This tendency becomes pronounced at about 18% of chlorine, and when chlorwax containing about 22% of chlorine is used, the resulting product is a rubbery mass practically insoluble in oil and very difiicult to remove from'the reaction vessel. On account of its lack of oil solubility, this product is practically useless for the purpose intended. At the same time, increases in chlorine content cause thewax substituted phenol formed from the chlorwax to be less stable at elevated temperatures. Below 12% of chlorine, the fleprmsant ability of the product falls of! to a marked degree. For these reasons it is preferred to use chlorwax containing about 14% of chlorine, or at least between 12% and 14%.

In accomplishing the reaction, phenol and chlorwax may be mixed together at a temperature varying from just above the melting point of the chlorwax to not over 150 F. The preferred proportionsare one'molecular amount of phenol to a sufllclent proportion of chlorwax to contain four atomic proportions of chlorine. The admixed phenol and chlorwax are heated to about 150 F., and anhydrous aluminum chloride introduced. The amount of aluminum chloride used should be about 3% by weight of the chlorwax. While adding this reagent, the mixture should be actively stirred and the rate of addition should be sufilclently slow to avoid violent foaming. During the addition of the aluminum chloride, the temperature should be held at about 150 F.

. After the addition of the aluminum chloride has 350 -F. will occupy approximately two hours from the time of adding the aluminum chloride, and the reaction mixture should have substantially ceased to emit hydrochlorlc acid gas when the final temperature is reached. If it has not done so, it may be held at 350 F. for a short time to allow completion of the reaction, but it should anew-lea not be heated appreciably above 350 F., nor should it be held for any extended length of time atthat temmrature.

The ratio of one molecular proportion of phenol to sufiicient chlorwax to contain four atomic proportions of chlorineis another important factor in producing the desired product. The eflectiveness of the depressant products increases as the ratio of chlorwax to phenol increases until a ratio of three atomic proportions of chlorine to one molecular proportion of phenol is reached. The

. derivative having four atomic proportions of chlorine to one molecular proportion of phenol is slightly less eflective but is more stable at elevated temperatures, however, and hence is preferred, particularly for use in internal combustion engines, such as automotive engines.

The percentage of aluminum chloride used is likewise not susceptible to wide variations if the most desirable products are to be obtained. When less than 3% of aluminum chloride is used,

- (based on chlorwax) it is diflicult to complete the minum chloride than is necessary is uneconoml-' cal and causes difliculty in purifying the final product. The effectiveness of the final material depends much upon the form of molecule of the wax ingredient, and any splitting, cracking, or shortening of this molecule immediately lessens the value of the product. Three per cent of aluminum chloridewill secure proper reaction with a minimum of 'wax-splitting and is, for that reason, preferred.

The use of solvents of a hydrocarbon nature to expedite the above reaction, especially light solvents such as kerosene, or those containing unsaturated hydrocarbons, is to be avoided. A portion of such solvents may be substituted into the product, in place of the desired wax radical, and the presence of such short chain alkyls is highly detrimental. It is preferable to work entirely without solvents.

The manner of carrying out the reaction, especially with respect to temperature and relation of time and temperature, is of the utmost importance. To recapitulate, it is preferred to introduce aluminum chloride at about F., and afterwards heat to a maximum of 350 F.

over a period of about two hours, raising thetemperature not more than a degree per minute between 250 F. and 350 F. Below about 150 F. only a mild reaction will result from the addition of 3% aluminum chloride to the phenol and ohlorwax mixture. At 150 F. a more violent reaction occurs, but the evolution of hydrochloric acid soon ceases. If the resulting product is chemically examined it will be found that little or no alkyl substitution of the phenol has taken place. Instead a phenate type of compound seems to have been formed.

Upon raising. the temperature, evolution of hydrochloric acid is resumed at about 200 F. and alkyl substitution appears to begin. Raising the temperature at the rate of one degree per minute 15 D substantial completion oi! the reaction by the time 350 F. is "reached. Substantially lower'rates oi heating and/or exposure to temperatures greater than 350 1". tend to bring about conditions wherein the cracking effect of the aluminum chloride on the wax is'sumciently great to impair the effectiveness of the product as a depressant. Addition of aluminum chloride at temperatures higher than about 150 F. also result in decreased eflectiveness, probably due to wax-splitting.

The product at this point is a good depressant, but under conditions of use does not remain'so and rapidly loses its effect. Apparently the aluminum isstill combined in the product makingit in part a wax substituted aluminum phenate, for the aluminum cannot be .removed by settling or centrifuging, and the product is clear rather than opaque or even cloudy.

To properly purify the product, it must be treated with something that is capable of hydrolyzing out the aluminum, which then combines with chlorine which remains dissolved in the mixture to reform aluminum chloride. When washed -with. water, the hydrolization apparently takes place, but diflicultly separable emulsions are formed, and'even when the washing is repeated a great number of times until the washings finally are neutral, the product is still not of the desired purity. 1

If instead, however,-;water containing an alcohol, such as butanol, is used and the product washed a halt dozen times with equal volumes of water, each containing about 2% butanol, (based on product), the aluminum and chlorine are both' removed. The washing should be accomplished with vigorous stirring and at relatively high temperatures, say of the order of 175 F. The first two or three washes, if desired, may be pure water without alcohol. The'washing should be continued until the product is sufficiently free from aluminum, etc., to satisfy a requirement of 0.02% maximum ash content. Emulsion troubles in washing, and likewise instability of the final product, increase rapidly with increases in percentage of aluminum chloride used in its preparation. The properties of the pour depressant product so prepared are substantiallyas follows:

Pour about F. Conradson carbon about 1.5% Visc. Saybolt at F. about 1930 seconds Visc. Saybolt at 210 F. about 300 seconds Ash-maximum about 0.02%

Mean molecular weight about 1000 By making the variations, in conditions that bon atoms and those having for their aryl nuclei,

such compounds as naphthols, anthrols, resorcinol, hydroquinone, chlorphenol, or any other material or mixture of materials that may be classified as oxyaromatic, that is, having oxygen atoms directly linked to the carbon atoms of a benzene ring. Diphenyl ether, naphthyl methyl ether, and benzyl phenol may be cited as still further examples.

made with any combination of these alkyl and oxyaromatic starting materials. Experiments inthe proportions are such thatwax containing oils. molecular weight oi phenol, this will cause Insofar as has been deter-' -mined, satisfactory stable compositions may be dicate, however, that all ofsuch'materials will not function as depressants for the'pour point or 'I'lhe present application is a division or applicationserial Number51,909, filed November 27,

1935. I claim: 1. A method of steps or: mixing together a chlorinated 'alkyl compound having a molecular weight about that of petroleum wax containing from about 12'per cent to about 14 per cent chlorine and an oxyslowly raise the temperature of the mixture tobetween 200 F. and 350 F. until the evolution of hydrogen chloride has substantially ceased; then discontinuing the heating and washing with forming stable alkyl-substi-' tuted oxyaromaticcompounds that comprisesthe water containing an alcohol to remove aluminum and purify the product,

2. A method of forming stable alkyl-substituted oxyaromatic compounds that comprises the steps of: mixing together a chlorinated alkyl compound having a molecular weight about that of petroleum wax containing from about 12 per cent to about 14 per cent chlorine and an oxy-- aromatic compound; heating the mixture and adding a few per cent or aluminum chloride ata temperature not in excess of F.; heating,

alter the addition of the aluminum chloride, to slowly raise the temperature or the mixture over a period 01' about two hours to a temperature '0! about 350 F. until the evolution of hydrogen chloride has substantially ceased; then discontinuing the heating and washing with water containing an alcohol to remove aluminum and purl fy'the product.

3. A method 01' forming stable alkyl-substitutedoxyaromatic compounds that comprises the steps oi: mixing together a chlorinated alkyl compound having a molecular weight about that of petroleum wax containing from about 12 per cent to about 14 per cent chlorine and an oxyaromatic compound in the ratio or about one molecular proportion of oxyaromatic compound to a quantity of the chlorinated alkyl compound containing about four atomic proportions of chlorine; heating the mixture and adding a few per cent of aluminum chloride at a temperature not in excess of 150 F.; heating, after'the addition of the aluminum-chloride, to'slowly raise the temperature or the -mixture to between 200 F. and 350 F. until the evolution of hydrogen chloride has substantially ceased; then discontinuing the heating and washing with water containing an alcohol to remove aluminum and puri- -fy the product.

tity of the chlorinated alkyl compound containing about four atomic proportions of chlorine; heating the mixture and adding a few per cent of aluminum chloride at a temperature not in excess o1 150 F.; heating, after the addition or the aluminum chloride, to slowly raise the temperature of themixture over a period or about two 7 hours to a temperature of about 350 F.; then discontinuing the heating and washing with water containing an alcohol to remove aluminum and purify the product.

5. As a new composition of matter, wax-substituted phenol prepared by mixing chlorinated paraflin wax and phenol, adding anhydrous aluminum chloride thereto at a temperature of about 150 F., heating the mixture to 250 F., raising the temperature from 250 F. to about 350 F. at the rate of approximately one degree per minute, and discontinuing the heating, and then washing the product with water containing an alcohol to purify the same and remove aluminum, the chlorinated Wax containing about 14 per cent of chlorine and the proportions of the ingredients being such that about four atoms of chlorine are originally presentin the chlorinated wax for each taining an alcohol to purify same to an ash con tent not substantially in excess of 0.02%, the

chlorinated wax containing about 14% of chlorine and the proportions of the ingredients being such that about four atoms of chlorine are originally present in the chlorinated wax for each molecule of phenol, aluminum chloride being used in the proportion of approximately 3%, based on chlorinated wax, said wax-substituted phenol being capable of depressing the pour point of oilwax mixtures.

7. A method of making wax substituted phenol, comprising the steps of mixing chlorinated paraffin wax and phenol, adding anhydrous aluminum chloride thereto at a temperature of about 150 F., heating the mixture to a temperature oi about 250 F. during a period of about 20 minutes, thereafter raising the temperature at the rate or approximately 1 per minute to about 350 F.,

, and discontinuing the heating, washing the prodpresent in the chlorinated wax for each molecule of phenol, and the amount of aluminum chloride used being about 3% based on the chlorinated wax.

comprising the steps of. mixing chlorinated par aflin wax and phenol, adding anhydrous aluminum chloride thereto at a temperature of about 150 F., heating the mixture to a temperature of about 250 F. during a period of about 20 minutes, thereafter raising the temperature at the rate of approximately 1 per minute to about 350 F., discontinuing the heating, washing the reaction product with water containing an alcohol to purify same to an ash content not substantially in excess of 0.02%, the chlorinated wax containing about 14% of chlorine and the proportions of the ingredients being such that about four atoms of chlorine are originally-present in the chlorinated wax 'for each molecule of phenol, and the 8. A method of making wax-substituted phenol,

amount of aluminum chloride used being about 3% based on the chlorinated wax.

9. A method for making a wax-substituted phenol, comprising the steps of mixing chlorinated parafiin wax, containing between about twelve per cent and about fourteen per cent chlorine, with a phenol in the ratio of one molecular proportion of phenol to a quantity of chlorinated wax containing about four atomic proportions of chlorine; adding anhydrous aluminum chloride to the mixture at a temperature of about 150 F. in an amount corresponding to from about three per cent to about five per cent by weight of chlorinated wax; slowly heating the mixture to a temperature between 200 F. and 350 F. until evolution of hydrogen chloride has substantially ceased; and then washing the reaction mixture with water containing an alcohol to remove aluminum and purify the product.

10..As a new composition of matter, a waxsubstituted phenol prepared by mixing chlorinated Paramn' wax, containing between about twelve ,and about fourteen per cent chlorine, with a phenol in the ratio of one molecular proportion of the phenol to a quantity'of chlorinated wax containing about four atomic proportions of chlorine; adding anhydrous aluminum chloride to the mixture at a temperature of about 150 F;

in anamount corresponding to from about three per cent to about five percent by weight of the chlorinated wax; slowly heating the mixture to a temperature between 200 F. and 350 15. until evolution of hydrogen chloride has substantially chlorine are originally present in the chlorinated wax for each molecule of phenyl and there is also present about 3 per cent of aluminum chloride based on the chlorinated wax.

12. As a new composition of matter, a wax-substituted phenol prepared from chlorinated paraffln wax, unsubstituted phenol and anhydrous aluminum chloride by mixing at around 150 F. and heating to around 350 F. over a period of about two hours and thereafter adding water to the mixture to effect removal of the aluminum chloride, the chlorinated wax containing around 14 per cent of chlorine and the proportions of the'ingredients being such that around four atoms of chlorine are originally present in the chlorinated wax for each molecule of phenol and there is also present about 3 per cent of aluminum chloride based on the chlorinated arcaaaa of chlorine and the proportions oi the ingredients being such that about four atoms of chlorine are cent based on the chlorinated wax.

14. As a new composition of. matter, a substantially pure poly-wax-substituted phenol otherwise unsubstituted formed by interacting chlorinated paraffin wax and phenol with heating in the presence of aluminum chloride at a temperature reaching about 350 F. sufficiently high to cause alkylation and adding water thereto to effect removal of the aluminum chloride.

15. As a new composition of matter, a substan tially pure poly-wax-substituted phenol otherwise unsubstituted formed by interacting chlorinated parafiin wax and phenol with heating in the presence of aluminum chloride at a temperature sufiiciently in excess of 200'. F. to cause a substantial alkylation and adding water thereto to eii'ect removal of the aluminum chloride, said wax-substituted phenol having an ash content of not more than around 0.02 per cent, the said product being efiective when incorporated in minor proportion in a mineral oil of high pour point to substantially depress the pour point thereof.

16. As a new composition of matter, a substantially pure poly-wax-substituted phenol otherwisaunsubstituted formed by interacting chlorinated paraffin wax and phenol with heating in the presence of aluminum chloride at a temperature sufiflciently in excess of 200 F. to cause substantial alkylation and washing the reaction product with a mixture of alcohol and water to effect removal of. the aluminum chloride, said wax-substituted phenol having an ash content of not more than around 0.02 per cent and being efiective when incorporated in a mineral oil oi high pour point to substantially depress the pour point thereof.

1'7. As a new composition of matter, a substantially pure poly-wax-substituted phenol otherwise unsubstituted formed by interacting chlorinated paraffin wax and phenol, in proportions such that at least three atomic proportionsot chlorine are present in the original materials for each mol of phenol, with heating in the presence of aluminum chloride at a temperature sufliciently in excess of 200 F. tocause substantial alkylation, and adding water thereto to effect removal of aluminum chloride, said wax-substituted phe nol having an ash content or not more than added in a around 0.02 per cent and being effective when incorporated in a mineral oiloi high pour point to substantially depress the pour point thereof.

18. As anew composition of matter, a substantially pure poly-wax-substituted phenol otherwise unsubstituted formed by interacting chlorinated paraflin wax andphenol, in proportions such that" about four atomic proportions of chlorineare present tin the original materials for each moi of phenol yvith heating in the presence of aluminum chloride at a temperature sumciently-high to cause substantially alkylation, and adding water'thereto to efiect removal of the aluminum chloride. said wax-substituted phenol having an ash content of not more than around 0.02 per cent and being efiective when added in a minor proportion to a mineral oil of. high pour point to substantially depress the pour point of such oil.

1'9. As a newcomposition of matter, a sub stantially pure poly-wax-substituted phenol otherwise unsubstituted formed by interacting chlorinated parafiin wax and phenol withheating in the presence of aluminum chloride at a temperature of from about 200 F. to about 350 F. suificiently high to cause substantial alkylation as indicated by substantial cessation of hydrochloric acid evolution, and adding water thereto to Iect removal of aluminum chloride, the chloral.- ated wax containing from about 12 per cent to about 14 percent chlorine and the proportions of ingredients being such that about three to four atoms of chlorine are originally present in the chlorinated wax for each molecule of phenol tially pure poly-wax-substituted phenol other-- wise unsubstituted formed by interacting chlorinated para wax and phenol with heating in the presence oi. aluminum chloride at a ternperature in excess of about 200 F. s'ufflciently high to cause substantial alkylation and adding water thereto to effect removal of aluminum chloride, the said product being effective when minor proportion to a mineral oil of high pour point to substantially depress the pour point of said oil.

- ORLAND M.. 

